Zeolite catalytic synthesis of high‐performance jet‐fuel‐range spiro‐fuel by one‐pot Mannich–Diels–Alder reaction

Abstract

A one-pot Mannich-Diels-Alder reaction was developed for synthesis of highperformance jet-fuel-range spirocycloalkane with an overall yield of 71.6% from biomass and petroleum derived cyclopentanone, formaldehyde, and cyclopentadiene. HZSM-5 zeolite with Si/Al molar ratio of 130 exhibits much higher catalytic activity, along with good recycling ability. Over it, a high selectivity (81.6%) and yield (80.9%) of target adduct is achieved with almost complete conversion of cyclopentanone, attributed to the synergy effect of appropriate ratio of Lewis to Brønsted acid sites and mass transfer effect of porous zeolite. More importantly, after hydrodeoxygenation, the resultant spirocycloalkane has much higher density and volumetric neat heat of combustion (0.952 gÁml −1 , 40.18 MJ L −1) than the wildly used JP-10 fuel (0.936 g ml −1 , 39.41 MJ L −1). This work provides a promising route to produce high-performance jet-fuel-range hydrocarbons through co-conversion of biomass and petroleum derivatives.

Review on the Relationship Between Liquid Aerospace Fuel Composition and Their Physicochemical Properties

“…Therefore, efforts have been exerted to synthesize high-density fuels that have a multiple-ring structure, such as RJ-4 (0.94 g/cm 3 ), a mixture of exo-and endo-tetrahydrodimethylcyclopentadiene synthesized by hydrogenation of dimethylcyclopentadiene, and JP-10 (0.936 g/cm 3 ) that is an almost pure component of exotetrahydrodicyclopentadiene synthesized by hydrogenation of endo-dicyclopentadiene (endo-DCPD) and catalytic isomerization [32][33][34]. Spiro-hydrocarbon fuels with additional rings can exhibit increased density; a high density of 0.952 g/cm 3 was reported for spiro[cyclopentane-1,2′norbornane] (C 11 H 18 ) synthesized by the zeolite catalytic Mannich-Diels-Alder reaction of biomass and petroleumderived feedstocks [35], whereas the density of spiro [4,5] decane (C 10 H 18 ) can reach 0.870 g/cm 3 [36]. Notably, liquid diamondoid fuels, such as alkyl adamantanes, alkyl diamantanes, and alkyl triamantanes, also present a high density due to their compact internal molecular structure [37][38][39][40][41].…”

“…Given the positively linear correlation between the volumetric NHOC and fuel density, many studies attempted to synthesize high-density fuels to increase the volumetric NHOC and expand the flight distance [32,35,36,69,74,75]. A crucial step toward high-density fuels is the synthesis of RJ-4 (39.0 MJ/L) with a density of 0.940 g/ cm 3 [34].…”

Synthesis of jet fuel range high-density polycycloalkanes with vanillin and cyclohexanone

“…In the past few decades, the catalytic conversion of renewable, CO 2 neutral, cheap, abundant and inedible lignocellulose to fuels 1 and chemicals 2 has drawn tremendous attention. Jet fuel is one of the most demanded transportation fuels.…”

Synthesis and Performance of Strained Multicyclic Hydrocarbons as Highly Potential High-Energy-Density Fuels

“…Advanced aerospace vehicles featured with high flight speed, long flight range, and heavy payload require advanced fuels to provide sufficient propulsion . The design and synthesis of high-energy-density fuels are attracting intensive interest because they can provide more propulsion power. − Generally, high-energy-density fuels are difficult to obtain from petroleum refineries and must be synthesized by chemical reactions. Conventional fuels are synthesized with five- or six-membered cyclic hydrocarbons, such as RJ-4, − JP-10, − RJ-5, RJ-7, ,, and spiro fuels, ,, whose density is significantly higher than that of alkanes with the same carbon number.…”

“…The design and synthesis of high-energy-density fuels are attracting intensive interest because they can provide more propulsion power. − Generally, high-energy-density fuels are difficult to obtain from petroleum refineries and must be synthesized by chemical reactions. Conventional fuels are synthesized with five- or six-membered cyclic hydrocarbons, such as RJ-4, − JP-10, − RJ-5, RJ-7, ,, and spiro fuels, ,, whose density is significantly higher than that of alkanes with the same carbon number. However, the gravimetric net heat of combustion (NHOC) of five- or six-membered cyclic hydrocarbons decreases with the increase of density because of the increased C/H ratio, , which partly counterparts the benefit of increased density and suppresses the further increase of volumetric net heat of combustion (VHOC).…”